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Cooperativity and Anticooperativity in Ion‐Water Interactions: Implications for the Aqueous Solvation of Ions
Author(s) -
Sauzade la Vega Arturo,
RochaRinza Tomás,
GuevaraVela José Manuel
Publication year - 2021
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.202000981
Subject(s) - cooperativity , solvation , chemistry , chemical physics , ion , molecule , aqueous solution , hydrogen bond , interaction energy , solvation shell , computational chemistry , organic chemistry , biochemistry
Non‐additive effects in hydrogen bonds (HB) take place as a consequence of electronic charge transfers. Therefore, it is natural to expect cooperativity and anticooperativity in ion‐water interactions. Nevertheless, investigations on this matter are scarce. This paper addresses the interactions of (i) the cations Li + , Na + , K + , Be 2+ , Mg 2+ , and Ca 2+ together with (ii) the anions F − , Cl − , Br − , NO 3 − and SO 4 2− with water clusters (H 2 O) n , n=1–8, and the effects of these ions on the HBs within the complete molecular adducts. We used quantum chemical topology tools, specifically the quantum theory of atoms in molecules and the interacting quantum atoms energy partition to investigate non‐additive effects among the interactions studied herein. Our results show a decrease on the interaction energy between ions and the first neighbouring water molecules with an increment of the coordination number. We also found strong cooperative effects in the interplay between HBs and ion‐dipole interactions within the studied systems. Such cooperativity affects considerably the interactions among ions with their first and second solvation shells in aqueous environments. Overall, we believe this article provides valuable information about how ion‐dipole contacts interact with each other and how they relate to other interactions, such as HBs, in the framework of non‐additive effects in aqueous media.